Comparison of drag reduction, rheology, microstructure and stress-induced precipitation of dilute cationic surfactant solutions with odd and even alkyl chains

Cationic surfactant systems of different alkyl chain lengths with counterion, C_nTAC(5 mmol/l)/3-Cl-Benzoate(12.5 mmol/l) (n=15, 16, 17, 18), were investigated for drag reduction, rheological behaviors, microstructure, and stress-induced precipitation. These are the first measurements of these characteristics for odd chain length (C₁₅ and C₁₇) quaternary ammonium surfactants. The lower and upper effective drag reduction temperature limits, viscoelasticity, and stress-induced precipitation temperature increased with alkyl chain length. Krafft temperature, critical turbidity temperature, and lower drag reduction effectiveness temperature limit showed a zigzag odd-even effect, while the stress-induced precipitation temperature did not. Light microscopy and cryo-TEM showed that cooling the C₁₅ solution below 20 °C produced crystals, while above that temperature threadlike micelles were present. The same was true for the solutions of C₁₈ that had threadlike micellar network microstructures when clear and crystals formed upon cooling. Micellar solutions can remain in a homogenous metastable state at a temperature below the Krafft temperature and above the critical turbidity temperature for days without external disturbance. Imposition of flow stress causes the systems to overcome the energy barrier and precipitate.